Method of treating emulsions



W. F. VAN LOENEN METHOD OF TREATING EMULSIONS Jan. 23, 1934.

Filed May 21, 1952 WILLIAM EVAN LOENEN /N QM w,

ATTO EV Patented Jan. 23, 1934 NETEEE 3'? TE lditiw FATE William F. Van Loenen, Buena Park, Califi, assignor to L. Blake-Smith, San Francisco,

Calif.

Application May 21, 1932. Serial No. 612,846

14) Claims.

The object of my invention is to provide a method for treating emulsions with granular solid bodies which are insoluble or slowly soluble in any of the constituents of the emulsion and which produce their resolving effect by reason of a preferential wettability for one or other of the emulsion constituents.

My pre ent invention does not comprehend any new or novel treating agent but applies equally to all known agents and to such as may hereafter be discovered, provided only that such agent be a comminuted solid and that it have a specific gravity materially different from that of the emulsion. My invention, as herein disclosed, comprises a method of so applying agents of this class to an emulsion as to produce the greatest eificiency and rapidity of action consistent with the properties of the agent.

It is well known that some solid substances have a strong surface attraction for the aqueous constituent of an oil-water emulsion and a very much lower attraction for the oily constituent, while other materials have at least as great an attraction for oil as for water and in some cases an even greater attraction. It is known to treat emulsions with sand, hay, excelsior and other substances which, when once wet-ted with water, will thereafter lay hold of water particles with which they may come into contact and tend to coalesce such particles into larger drops. It has also been discovered that when a mixture of minerals such, for instance, as silica and iron sulfid (the first having a superior attraction for water and the second a superior attraction for oil) is agitated with an oil-water emulsion under suitable condition, the emulsion is resolved into its constituents and will separate by gravitation into a supernatant oily layer and a subnatant aqueous layer. The breaking of emulsions by the use of these and similar substances is the invention of others and I lay no claim thereto, my present invention residing solely in the manner in which the treat-- ing agent is applied to the emulsion.

It is also known to treat emulsions with granular solids by various physical methods; such as to form the grains into a bed or pack and pass the emulsion therethrough (percolation) to form a layer of the grains on a filter cloth and pass the emulsion through such layer under pressure (filtration), or to maintain the grains in suspension in a turbulent mass of the emulsion and its resolution products by stirring with paddles, agitating with streams of gas or air, circulatory pumping or other means of maintaining the fluid in the state of agitation required to suspend the K relatively heavy grains employed.

In all of these methods, as well as in that which I hereinafter describe, the emulsion is resolved by relative movement of the solid grains and the dispersed liquid particles of the emulsion. In percolation and filtration the grains are held in a fixed position and the suspended particles collide with them in passing through the interstices of the pack or layer. In the agitation systems turbulence is utilized to raise the relatively heavy grains from the bottom of the retaining vessel and to cause more or less rapid movement of the grains through the liquid mass, by which the grains are caused to collide with the dispersed liquid particles.

The percolation and filtration methods have signally failed to give satisfactory results in the treating of emulsions. First, if any worth-while contact between grains and particles is to be effected, the grains must be relatively small and the interstices correspondingly narrow, and as many emulsions, particularly the more resistant ones, are extremely viscous, the throughput of such packs is small. Second, and also because of the necessarily fine interstices, the clay and other foreign matter which is almost invariably present in the emulsion clogs the filter so rapidly as to make its effective life very short. Third, the rapid passage of the emulsion through these narrow channels sets up the very turbulence which it is my object to avoid.

The agitation methods have produced better results, but these leave much to be desired. It is impossible to project the solid grains upwardly through the liquid mass without setting up a violent agitation, not only of the emulsion itself but also of the resolution products. This agitation tends strongly to reemulsify the products as they are set free, and while this reemulsir'lcation will seldom be complete in the earlier stages of the treatment, it offsets and destroys part of the initial resolving effect. Further, as the treatment proceeds and the proportion of dispersed liquid decreases, the reemulsifying efiect due to agitation approaches constantly more closely to the resolving effect until the two come to a balance at some point short of complete resolution. With some readily resolved emulsions this point of balance may be within commercial limits, but with others more difficult to separate it may be, and often is, impossible to effect a commercially complete separation.

My improved method of applying granular solids to emulsions bears no relation whatever to percolation or filtration, but it is comparable with the agitation methods in the single sense that resolution is efiected by moving the grains through a mass of liquid instead of moving the liquid through a mass of grains. It embodies, however, an entirely new concept in this respect, that instead of keeping the liquid mass in a state of turbulence in order to produce the requisite movement of the grains into contact with the dispersed liquid particles, I maintain the liquid in the nearest possible approach to a state of rest and produce the relative movement by applying mechanical force to the solid as a substantially separate material. This is in contrast to all other methods of accomplishing contact and relative movement, in which the mechanical force is applied directly to the liquid, as in percolation or filtration, or in which the mechanical force is applied indiscriminately to liquid and solid together, as in the use of paddles, air lift or pachuca tube.

In my improved method such movement of the liquid as may take place during the treatment is due primarily to the movement of the relatively small volume of solid through or within the liquid, and may readily be restricted within such limit as to avoid turbulence. In the prior methods above mentioned a very rapid movement of the liquid, always approaching and usually passing the lower limit of turbulence, is requisite to maintain effective contact between liquid and solid.

My invention of method can be given'practical application in two forms which produce the same ultimate result by different movements within the mass of liquid undergoing treatment.

In the form described in an application filed by me on May 21, 1932 under Serial No. 612,845, the grains of solid agent used are specifically heavier than the heavier liquid of the emulsion; so that they come to rest on the bottom of the retaining vessel, from which position they are transferred by mechanical means to a higher level or even to a point above the liquid body, being there released to travel downwardly through the liquid to the bottom of the vessel.

In the form described in the instant application the grains of solid agent are specifically lighter than the lighter liquid of the emulsion and come to rest on the upper surface of the liquid body, from which position they are mechanically transferred to a lower level in the liquid body, being there released to again rise to the surface.

By operating in the manner hereinafter described I gain several important advantages which manifest themselves in an increase of as much as ten times in the speed with which any given emulsion may be broken by any given solid agent, in the ability to completely resolve many stubborn emulsions which heretofore could not be reduced to commercial specifications by any known method, and in the ability to demulsify at much lower temperatures than any heretofore used. The operation differs from the prior art agitation meth ods in the following particulars:

(a) The removal of the granular solid from the surface of the liquid body to the preferred level therein is positive and the solid may be circulated very rapidly, thus greatly increasing its effectiveness of contact.

(1)) The rapid circulation of the grains is accomplished without setting up a state of turbulence in the liquid mass, thus permitting the resolution products to stratify as they are set free.

(0) In avoiding turbulence, reemulsification is completely avoided.

((1) The granular solid may be removed from the surface stratum with only so much liquid as actually adheres to the grains, and thus each grain is free to contact with the particles of dispersed liquid in the layer of emulsion to which the grains are removed. When the liquid mass is agitated to produce relative movement, the greater part of the grains are enclosed in relatively large drops of the upper liquid layer and only such grains as lie on the immediate surface of such drops can contact with dispersed particles, those in the interior of the drop being completely withdrawn from effective contact.

(9) The separated solid grains gravitate through the emulsion stratum in only an upward direction, coalescing and collecting the dispersed liquid in their passage." If the dispersed liquid be lighter than the continuous liquid, the dispersed liquid will form the upper stratum and the upward gravitation of the grains will aid in conveying the coalesced liquid into its proper stratum. This advantage will not be realized in the case of oil-water emulsions or others in which the dispersed liquid is the heavier and forms the lower layer.

(f) Pertoleum emulsions, which constitute the greater part of the emulsions commercially treated, almost always contain foreign bodies (clay, insoluble soaps or salts of naphthenic acids, colloidal bitumens and the like) which act as emulsifying agents. On the resolution of the emulsion these bodies tend to adhere to and coat over the solid grains, destroying their demulsifying power. By moving the coated grains through a maintained layer of water, and particularly by moving them in such manner as to cause the grains to abrade each other, this coating is washed off and the effectiveness of the solid indefinitely prolonged.

(9') By avoiding the use of gas or air to produce agitation, the formation of froth is avoided.

(h) In, mechanically moving portions of the mass of grains which accumulates on the surface of the liquid I am not limited to any particular size of grain but can use fragments of treating material of such size as to have a high relation of mass to surface and which will therefore rise rapidly through even very viscous emulsions. It is very diiiicult to produce intermixture of light treating agents with viscous emulsions by agitation, unless such agents be ground so finely that they separate from the emulsion only very slowly.

(i) Inavoiding turbulence each layer of resolution product is maintained relatively free from drops of liquid belonging in the other layer and thus separation proceeds along with resolution while. in agitation systems, the products are kept constantly intermingled and a successive separation step is required.

(7') The resolution products are at all times in the form of separated layers which may be partially withdrawn without any material removal of either solid or emulsion, the continuous operation of the apparatus being thus greatly facilitated.

In order to point out more clearly the functional distinction between the agitation systems heretofore used and the novel method which I propose, reference is made to the attached drawing, in which Fig. 1 is a diagrammatic representation of the i aid.

In these diagrams the dispersed liquid is assumed to be heavier than the continuous liquid and the solid grains to be lighter than either liquid.

Referring to Fig. 1, A is the retaining vessel and B an accumulating layer of granular solid, F is an ordinary bucket elevator arranged to dip into the layer of grains as at G, to gently draw them down through the liquid as at H, and to discharge them as at I, either above or below the parting line R between the two liquid layers. The liquid body is shown as consisting of two strata, an upper oil layer J from which emulsion is gradually being removed by resolution and which in its upper portion may be substantially free from emulsion, and a water layer K. The arrows in this diagram indicate the upward travel of the solid grains only, the liquid being substantially undisturbed.

Referring to Fig. 2, the retaining shell A is in the form of a cylinder which is being slowly rotated counter-clockwise. Vanes L entrap grains from the mass accumulating at B and discharge them at a lower point into the oil layer J as indicated at N or into the water layer K as indicated at O. The arrows indicate the movement of the granules only, the oil and water strata J and K being substantially undisturbed. By using bent or curved vanes as indicated at O and P or by rotating at such speed as to produce a material centrifugal action, the final point of delivery of the grains into the liquid may be brought to either side of the lower center line of the shell.

It will be obvious that the separate removal of the granular solid from the upper to the lower part of the retaining vessel may be produced by several well-known mechanical means, of which but two are above indicated, but I have obtained particularly satisfactory results with the apparatus represented by the diagram of Fig. 2. This apparatus is fully described and claimed in an application filed May 21, 1932 under Serial No. 612,847.

The functional characteristic of my invention broadly is that two separate horizontal zones are defined and maintained within the treating apparatus. In one of these zones the emulsion is contacted with and resolved by the treating agent, in the other the liquid of the dispersed phase is collected.

The functional characteristic of the form claimed in the present application is the removal of the granular solid from the upper surface of the liquid and its return to and distribution through the lower portion of the layer of emulsion, through which it passes upwardly to again collect at the top of the vessel.

Obviously, many circulating devices (including those indicated in Figs. 1 and 2) may be operated at speeds which will produce violent agitation of the liquid body and it is premised that the devices shown shall be operated at such low speed as will avoid undue agitation of the liquid. It is characteristic of my improved method that, as the granular solid is moved within the apparatus as a substantially separated body, there is no necessary relation between the rate of circulation and the speed of the circulating mechanism, the rate being increased to any desired extent without increase of speed by mere enlargement of the capacity of the buckets, vanes or other circulating device. This is not true in the agitation methods, where the mixing action varies with the velocity of the suspending medium.

While I do not restrict my invention to the treatment of petroleum emulsions, it being adapted to use with any emulsion or intimate mixture which may be resolved by means of solid granular agents, the characteristics of petroleum-water emulsions are so well known and the method is so well adapted to their treatment that I will describe the method in that connection, with the understanding that for oil in this description we may read the lighter liquid of any emulsion, and for water the heavier liquid thereof. The term granular solid in this description and in the claims includes any solid body having the property of resolving emulsions primarily by physical forces, such solid being natural or artificial, being sufiiciently hard and sufiiciently insoluble to retain its granular form in the described use, and being specifically lighter than the lighter liquid of the emulsion.

Figs. 1 and 2 show dissimilar devices func-v tioning in a substantially identical manner. Referring to Fig. 1, 10 is a stationary shell, which may be open or may be closed at the top as preferred. A pipe 11 controlled by a valve 12 serves to introduce emulsion from any source of supply not shown. A pipe 13 controlled by a valve 14: serves to withdraw coalesced water and a pipe 15 controlled by a valve 16 serves to withdraw cleaned oil. A deflector plate 20 prevents floating solids from entering the oil outlet pipe this may be a screen if preferred. Sight glasses 1'7 and 18 indicate respectively the upper level of liquid in the apparatus and the parting line between oil and water. A conventional bucket elevator 19, operated by means not shown, is arranged so that the buckets approach the top of the vessel and entrap bodies of granular solid, as at G, depressing these bodies through the liquid, as at H, and discharging them at any desired level, which may be above or below the parting level R.

The apparatus shown in Fig. 2 is the crosssection of a revolving cylinder in which the vanes L, N and O perform the same function as the buckets H of Fig. 2, the only difference being that in the apparatus of Fig. 2 the solids are carried down the side of the shell instead of through the center as in Fig. l. The shell in Fig. 2 may be provided with suitable inlet, outlet and level gauge connections, carried through a stationary plate fitted in the revolving heads.

In operating my method in either form of apparatus a suflicient dose of granular solid is placed in the shell, the dose being immaterial to the present invention so long as it is sufficient to maintain at least a small quantity of solids on the upper surface of the liquid during operation. Most emulsions treat more easily in the presence of a body of the dispersed liquid and in starting up a new apparatus it is desirable to introduce enough water, or a saline solution similar to that of the emulsion, to establish such body in ad- Vance, though, if preferred, it may be permitted to slowly accumulate by resolution and coalescence. The shell is then filled to the desired height with the emulsion to be treaetd, this height being preferably just above the oil outlet pipe 15.

The circulating mechanism is then started, the V The first condition favors the dispersion through the emulsion of coarser grains, which are more desirable than fine powders for use in this form of the invention.

In their upward travel (by gravitation) through the emulsion the grains collide with the dispersedv water particles and such of the grains as are preferentiallywater-wettable lay hold of the dispersed water particles and hold them in the form of a film until the grains are immersed in the water layer, with which the water films immediately coalesce. If any of the grains are preferentially oil-wettable, they lose all but an adsorbed skin of oil on passing into the water layer. The solid agent used may be preferentially water-wettable only, or may consist of two substances, one preferentially wetted by water, the other by oil.

By the constant removal of water from the emulsion layer and its coalescence with the water layer, the latter is constantly increased in volume and when the parting level reaches the desired height, a slow stream of water is withdrawn through pipe 13, this stream being so adjusted as to maintain the parting level constant in the sight glass.

By the removal of water from the emulsion layer, the upper portion of the oily layer is soon freed from emulsion and may be withdrawn through pipe 15 at such rate as to avoid withdrawal of unbroken emulsion. It is permissible to withdraw oil containing relatively large drops of water for settlement outside the treating ves sel, the capacity of the treater being thus materially increased when the gravity difference between the water and the oil is so slight that the coalesced water settles out more slowly than it is produced by resolution.

In either case the stream of entering emulsion is so adjusted as to equal the combined withdrawal of water and oil.

As the solid agents used are not consumed or waste away very slowly, the above described operation is continuous over long periods. It might also be made intermittent, were there any object in doing so, by treating a batch to the point of complete resolution and withdrawing the products, leaving the solid, and preferably the water layer also, for the treatment of the next batch.

I claim as my invention:

1. A method of treating an emulsion with granular solids specifically lighter than said emulsion: etsablishing in a vessel a liquid body of said emulsion and a body of said solids; mechanically conveying said solids in a substantially separated form from the level to which said solids gravitate to a lower level in said liquid body, and releasing said solids at said lower level to return by gravitation to first said level.

2. A method of treating an emulsion with granular solids having the property of resolving said emulsion into its constituents and being specifically lighter than said emulsion; establishing in a vessel a liquid body of said emulsion and a body of said solids; mechanically conveying said solids in a substantially separated form from the level to which said solids gravitate to a lower level in said liquid body; releasing said solids at said lower level to return by gravitation to first said level, and continuing said conveying and releasing until said emulsion is sufiiciently resolved.

3. A method of treating an emulsion with granular solids specifically lighter than said emulsion: establishing in a vessel a liquid body of emulsion to be treated and a body of said solids; mechanically conveying said solids from the upper to the lower portion of said liquid body, and there releasing them to rise through said liquid.

4. A method of treating an emulsion with granular solids specifically lighter than said emulsion and having the property of resolving said emulsion into its constituents: establishing in a vessel a liquid body of emulsion to be treated and a body of said solids; mechanically conveying said solids from the upper to the lower portion of said liquid body and there releasing them to rise through said liquid, and continuing said conveying and releasing until said emulsion is sufiiciently resolved.

5. A continuous method of treating an emulsion with granular solids having the property of resolving said emulsion into its constituents: establishing in a vessel a liquid body of said emulsion and a body of said solids; mechanically conveying said solids from the upper to the lower portion of said liquid body and releasing said solids to rise through said liquid body, whereby said emulsion is repeatedly contacted with said solids and is thereby resolved; withdrawing the resolved constituents at substantially the rate at which they are set free, and replenishing the supply of emulsion at substantially the rate at which it is resolved.

6. A method of treating an oil-water emulsion with granular solids having the property of resolving said emulsion into its constituents: establishing in a vessel a liquid body of said emulsion; contacting with said emulsion said granular solids; retaining in said vessel a layer of water beneath an oily layer containing emulsion; distributing in one of said layers a supply of said solids, said solids rising through said oily layer to the top of said liquid body; and continuously returning said solids from the top of said liquid body to the bottom of said oily layer while maintaining said layers substantially separated.

7. A method of treating an oil-water emulsion with granular solids having the property of resolving said emulsion into its constituents: establishing in a vessel 2. liquid body of said emulsion; contacting with said emulsion said granular solids; retaining in said vessel a layer of water beneath an oily layer containing emulsion; distributing in one of said layers a supply of said solids, said solids rising through said oily layer to the top of said liquid body; and continuously returning said solids from the top of said liquid body to said water layer while maintaining said layers substantially separated.

8. A continuous method of treating an emulsion with a granular solid specifically lighter than said emulsion: feeding emulsion to a liquid body in which resolution is effected by contact with said solid; withdrawing the products of said resolution at a combined rate substantially equal to the rate of said feed, and continuously contacting said solid with said liquid body by continuously mechanically conveying said solid from the upper to a lower portion of said body and distributing said solid through said lower portion to rise through said liquid body.

9. A continuous method of treating an oilwater emulsion with a granular solid specifically lighter than said emulsion; feeding emulsion to a liquid body in which resolution is effected by contact with said solid; withdrawing resolution products at such rate as to retain a layer of water underlying an oily layer in said liquid body; distributing said solid through said water layer to rise through both said layers, and continuously ,mechanically withdrawing said solid from over ers of the coalesced liquid and of incompletely resolved emulsion; passing said solid upwardly through said emulsion layer while maintaining said coalesced layer in a state of relative quiescence, and continuously withdrawing said solid from the upper part of said emulsion layer and returning it to a lower part of said emulsion layer to again pass upwardly therethrough.

WILLIAM F. VAN LOENEN. 

